CN110198796B - Three-dimensional (3D) printing - Google Patents

Abstract

In a three-dimensional (3D) printing method example, a metallic build material is applied. An adhesive fluid is selectively applied on at least a portion of the metal build material. The adhesive fluid includes a liquid carrier and polymer particles dispersed in the liquid carrier. The application of the metal build material and the selective application of the binder fluid are repeated to create a patterned green part. The patterned green part is heated to near the melting point of the polymer particles to activate the binder fluid and produce a cured green part. The cured green part is heated to a thermal decomposition temperature of the polymer particles to produce an ash part that is at least substantially free of polymer. The at least substantially polymer-free soot body component is heated to a sintering temperature to form a metal component.

Description

Three-dimensional (3D) printing

Background

Three-dimensional (3D) printing may be one additive printing method for fabricating three-dimensional solid parts from digital models. 3D printing is commonly used for rapid prototyping, mold generation, master generation, and small volume manufacturing of products. Some 3D printing techniques are considered additive methods because they involve the application of a continuous layer of material. This is different from conventional machining processes (which typically rely on the removal of material to produce the final part). 3D printing often requires solidifying or fusing build materials, which for some materials can be achieved using heat assisted extrusion, melting, or sintering, and for other materials can be achieved using digital light projection techniques.

Brief description of the drawings

Features of examples of the present disclosure will become apparent by reference to the following detailed description and drawings in which like reference numerals correspond to similar (although perhaps not identical) components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.

FIG. 1 is a simplified isometric schematic diagram of one exemplary 3D printing system disclosed herein;

fig. 2A-2F are schematic diagrams depicting the formation of a patterned green body part, a cured green body part, an at least substantially polymer-free gray body part, and a 3D metal part using examples of 3D printing methods disclosed herein;

fig. 3A and 3B are black and white photographs showing a cured green part (fig. 3A) and a 3D metal part (fig. 3B) formed by one example of the 3D printing method disclosed herein;

fig. 4A and 4B are black and white photographs showing another cured green part (fig. 4A) and another 3D metal part (fig. 4B) formed by another example of the 3D printing method disclosed herein; and

fig. 5 is a flow chart illustrating one example of a 3D printing method disclosed herein.

Detailed Description

In some examples of three-dimensional (3D) printing, a binder fluid (also referred to as a liquid functional agent/material) is selectively applied to one layer of build material, followed by the application of another layer of build material thereon. The binder fluid may be applied to the other layer of build material, and the processes may be repeated to form a green part (also referred to as a green body) of the 3D part that is ultimately to be formed. The binder fluid may include a binder that holds the build material of the green part together. The green part may then be exposed to electromagnetic radiation and/or heat to sinter the build material in the green part to form a 3D part.

Examples of 3D printing methods and systems disclosed herein utilize a binder fluid comprising polymer particles to produce patterned green part from a metallic build material, and also utilize heat to activate the polymer particles and generate a cured green part. The cured green part can be removed from the metal build material that is not patterned with the binder fluid without detrimentally affecting the structure of the cured green part. The extracted cured green part may then be debinded to produce an at least substantially polymer-free gray part, which may then be sintered to form the final 3D printed part/object.

The term "patterned green part" as used herein refers to an intermediate part having a shape representative of the final 3D printed part and comprising a metallic build material patterned with a binder fluid. In patterned green part, the metal build material particles may or may not be weakly bound together by one or more components of the binder fluid and/or by attractive forces between the metal build material particles and the binder fluid. In some cases, the mechanical strength of the patterned green part is such that it cannot be machined or extracted from the build material platform. Further, it is to be understood that any metallic build material that is not patterned with a binder fluid is not considered to be part of the patterned green part even if it abuts or surrounds the patterned green part.

As used herein, the term "cured green part" refers to a patterned green part that has been exposed to a heating process that initiates melting of the polymer particles in the binder fluid (which may be facilitated by the coalescing solvent), and may also facilitate evaporation of the liquid component in the binder fluid, such that the polymer particles form a polymer glue that coats the metal build material particles and creates or enhances bonding between the metal build material particles. In other words, a "cured green part" is an intermediate part having a shape representative of the final 3D printed part and comprising metal build material bonded together by at least substantially cured polymer particles of a binder fluid with which the metal build material is patterned. The cured green part is mechanically stronger than the patterned green part, and in some cases, can be machined or extracted from the build material platform.

It is to be understood that the term "green body" when referring to a patterned green body part or a cured green body part does not imply a color, but rather indicates that the part has not been fully processed.

As used herein, the term "at least substantially polymer-free gray green part" refers to a cured green part that has been exposed to a heating process that initiates thermal decomposition of the polymer particles, thereby at least partially removing the polymer particles. In some cases, the volatile organic components of the thermally decomposed polymer particles or generated from the thermally decomposed polymer particles are completely removed, and very little non-volatile residue from the thermally decomposed polymer particles may remain (e.g., < 1 wt% of the original binder). In other cases, the thermally decomposed polymer particles (including any products and residues) are completely removed. In other words, an "at least substantially polymer-free gray part" refers to an intermediate part having a shape representative of the final 3D printed part and comprising metallic build material bonded together as a result of i) weak sintering (i.e., low levels of necking between particles that are capable of retaining the part shape), or ii) small amounts of residual solidified polymer particles, or iii) capillary and/or van der waals forces resulting from removal of the polymer particles, and/or iv) any combination of i, ii, and/or iii.

It is to be understood that the term "gray body" when referring to a gray body part that is at least substantially free of polymer does not imply a color, but rather indicates that the part has not been fully processed.

The at least substantially polymer-free gray green part may have a porosity (due to polymer particle removal) similar to or greater than the cured green part, but that porosity is at least substantially eliminated during the transition to the 3D printed part.

The terms "3D printed part," "3D part," or "metal part" as used herein refer to a finished sintered part.

In the examples disclosed herein, the binder fluid comprises polymer particles dispersed throughout a liquid carrier of the binder fluid. When applied to a layer of metallic build material, the liquid carrier is capable of wetting the build material and the polymer particles are capable of penetrating into the microscopic pores of the layer (i.e., the spaces between the metallic build material particles). Thus, the polymer particles can move into the empty spaces between the metal build material particles. The polymer particles in the binder fluid may be activated or cured by heating the binder fluid (which may be accomplished by heating the entire layer of the metal build material to which the binder fluid has been selectively applied over at least a portion thereof) to near the melting point of the polymer particles. When activated or cured, the binder fluid forms an at least substantially continuous network that glues the metal build material particles into a cured green part shape. The cured green part has sufficient mechanical strength to withstand extraction from the build material platform without adverse effects (e.g., without losing shape).

Once extracted, the cured green part may be debonded by heating the cured green part to the thermal decomposition temperature of the polymer particles to thermally decompose the polymer particles. When at least a portion of the polymer particles thermally decompose, an ash blank component is formed that is at least substantially free of polymer. The at least substantially polymer-free ash blank component can then be heated to a sintering temperature to sinter the metallic build material particles and form a metallic component.

Referring now to FIG. 1, one example of a 3D printing system 10 is depicted. It is to be understood that the 3D printing system 10 may include additional components, and some of the components described herein may be removed and/or modified. Furthermore, the components of the 3D printing system 10 depicted in fig. 1 are not drawn to scale, and thus the 3D printing system 10 may have different sizes and/or different configurations than those shown herein.

Three-dimensional (3D) printing system 10 generally includes a supply 14 of metallic build material 16; a build material distributor 18; a supply of an adhesive fluid 36, the adhesive fluid 36 comprising a liquid carrier and polymer particles dispersed in the liquid carrier; an inkjet applicator 24 for selectively dispensing the adhesive fluid 36 (fig. 2C); at least one heat source 32, 32'; a controller 28; and a non-transitory computer-readable medium having computer-executable instructions stored thereon to enable controller 28 to: using the build material distributor 18 and the inkjet applicator 24 to iteratively form a plurality of layers 34 (fig. 2B) of the metallic build material 16 applied by the build material distributor 18 and having received the binder fluid 36, thereby generating a patterned green body part 42 (fig. 2E), and using at least one heat source 32, 32 ' to heat the patterned green body part 42 to about the melting point of the polymer particles, thereby activating the binder fluid 36 and generating a cured green body part 42 ', heating the cured green body part 42 ' to the thermal decomposition temperature of the polymer particles, thereby generating an at least substantially polymer-free gray body part 48, and heating the at least substantially polymer-free gray body part 48 to the sintering temperature to form the metallic part 50.

As shown in FIG. 1, printing system 10 includes a build area platform 12, a build material supply 14 containing metallic build material particles 16, and a build material distributor 18.

Build area platform 12 receives metallic build material 16 from build material supply 14. Build area platform 12 may be integral with printing system 10 or may be a component that is separately insertable into printing system 10. For example, build area platform 12 may be a module that is available independently of printing system 10. The illustrated build area platform 12 is also an example, and may instead be another support member, such as a platen, a manufacturing/printing bed, a glass plate, or another build surface.

The build region platform 12 may be moved in a direction as indicated by arrow 20, for example along the z-axis, so that the metal build material 16 may be delivered onto the platform 12 or onto a previously formed layer of metal build material 16 (see fig. 2D). In one example, when metallic build material particles 16 are to be delivered, the build region platform 12 can be programmed to advance (e.g., downward) enough that the build material distributor 18 can push the metallic build material particles 16 onto the platform 12 to form a layer 34 of metallic build material 16 thereon (see, e.g., fig. 2A and 2B). The build area platform 12 may also return to its original position, for example when a new part is to be built.

The build material supplier 14 may be a vessel, bed, or other surface that positions metallic build material particles 16 between the build material distributor 18 and the build area platform 12. In some examples, build material supply 14 may include a surface on which metallic build material particles 16 are supplied, for example, by a build material source (not shown) located above build material supply 14. Examples of sources of build material may include hoppers, augers, and the like. Additionally or alternatively, the build material supply 14 may include a mechanism (e.g., a delivery piston) to provide (e.g., move) the metal build material particles 16 from a storage location to a location to be spread onto the build area platform 12 or onto a previously formed layer of metal build material 16.

Build material distributor 18 may move over build material supply 14 and across build area platform 12 in a direction indicated by arrow 22, e.g., along the y-axis, to spread a layer of metallic build material 16 over build area platform 12. Build material distributor 18 can also return to a position adjacent build material supply 14 after spreading metal build material 16. Build material distributor 18 may be a doctor blade (e.g., a doctor blade), a roller, a combination of a roller and a doctor blade, and/or any other device capable of spreading metal build material particles 16 over build area platform 12. For example, build material distributor 18 may be counter-rotating rollers.

The metallic build material 16 may be any particulate metallic material. In one example, the metallic build material 16 may be a powder. In another example, the metal build material 16 can be sintered into a continuous body to form the metal part 50 when heated to a sintering temperature (e.g., a temperature of about 850 ℃ to about 1400 ℃) (see, e.g., fig. 2F). By "continuous body" is meant that the metal build material particles are fused together to form a single part that has little or no porosity and sufficient mechanical strength to meet the requirements of the desired final metal part 50.

While an example of a sintering temperature range is provided, it is to be understood that the temperature may vary depending in part on the composition and phase of the metallic build material 16.

In one example, the metallic build material 16 is a single phase metallic material composed of one element. In this embodiment, the sintering temperature may be below the melting point of the single element.

In another example, the metallic build material 16 is composed of two or more elements, which may be in the form of a single phase metal alloy or a multi-phase metal alloy. In these other examples, melting typically occurs over a range of temperatures. For some single phase metal alloys, melting begins just above the solidus temperature (the onset of melting) and is incomplete before exceeding the liquidus temperature (the temperature at which all solids have melted). For other single phase metal alloys, melting begins just above the peritectic temperature. The crystallization temperature is defined as the point at which a single phase solid transitions to a two phase solid plus liquid mixture, where solids above the crystallization temperature have a different phase than solids below the crystallization temperature. When the metallic build material 16 is composed of two or more phases (e.g., a multi-phase alloy made of two or more elements), melting typically begins when a eutectic or peritectic temperature is exceeded. The eutectic temperature is defined by the temperature at which a single phase liquid completely solidifies into a two phase solid. Generally, melting of a single-phase metal alloy or a multi-phase metal alloy begins just above the solidus, eutectic or peritectic temperature and is incomplete before the liquidus temperature is exceeded. In some examples, sintering may be performed at a temperature below the solidus temperature, the peritectic temperature, or the eutectic temperature. In other examples, the sintering is performed at a temperature above the solidus temperature, the peritectic temperature, or the eutectic temperature. Sintering above the solidus temperature is referred to as supersolidus sintering, and this technique may be desirable when larger build material particles are used and/or high densities are to be achieved. In one example, the build material composition can be selected such that at least 40 volume percent of the metallic build material is comprised of a phase having a melting point above a desired sintering temperature. It is to be understood that the sintering temperature may be high enough to provide sufficient energy to allow atomic migration between adjacent particles.

A single element or alloy may be used as the metallic build material 16. Some examples of metal build material 16 include steel, stainless steel, bronze, titanium (Ti) and its alloys, aluminum (Al) and its alloys, nickel (Ni) and its alloys, cobalt (Co) and its alloys, iron (Fe) and its alloys, nickel-cobalt (NiCo) alloys, gold (Au) and its alloys, silver (Ag) and its alloys, platinum (Pt) and its alloys, and copper (Cu) and its alloys. Some specific examples include AlSi10Mg, 2xxx series aluminum, 4xxx series aluminum, CoCr MP1, CoCr SP2, MaragingSteel MS1, Hastelloy C, Hastelloy X, Nickel alloy HX, Inconel IN625, Inconel IN718, SS GP1, SS 17-4PH, SS 316L, Ti6Al4V, and Ti-6Al-4V ELI 7. While several exemplary alloys have been provided, it is to be understood that other alloy build materials, such as PbSn braze alloys, may be used.

Any metallic build material 16 may be used that is in powder form at the beginning of the 3D printing method disclosed herein. Thus, the melting point, solidus temperature, eutectic temperature, and/or peritectic temperature of metal build material 16 may be higher than the ambient temperature (e.g., higher than 40 ℃) when performing the patterned portion of the 3D printing method. In some examples, the metal build material 16 may have a melting point of about 850 ℃ to about 3500 ℃. In other examples, the metallic build material 16 may be an alloy having a range of melting points. The alloy may include metals having melting points as low as-39 ℃ (e.g., mercury), or 30 ℃ (e.g., gallium), or 157 ℃ (indium), and so forth.

The metallic build material 16 may be composed of similarly sized particles or differently sized particles. In the example shown herein (fig. 1 and 2A-2F), the metal build material 16 includes similarly sized particles. The term "size" as used herein with respect to the metal build material 16 refers to the diameter of a substantially spherical particle (i.e., a spherical or near-spherical particle having a sphericity > 0.84), or the average diameter of an aspherical particle (i.e., the average of multiple diameters across the particle). Substantially spherical particles of this size have good flowability and can be spread relatively easily. As one example, the average particle size of the particles of the metal build material 16 may be about 1 μm to about 200 μm. As another example, the average size of the particles of the metal build material 16 is about 10 μm to about 150 μm. As yet another example, the average size of the particles of the metal build material 16 is 15 μm to about 100 μm.

As shown in fig. 1, printing system 10 also includes an applicator 24, which may contain a binder fluid 36 (shown in fig. 2C) as disclosed herein.

The adhesive fluid 36 comprises at least a liquid carrier and polymer particles. In some cases, the adhesive fluid 36 is composed of a liquid carrier and polymer particles, without any other components.

The polymer particles are sacrificial intermediate binders in that they are present in various stages of the green part 42, 42' being formed (shown in fig. 2E), and are subsequently ultimately removed from the green part 48 (by thermal decomposition), and thus are not present in the final sintered 3D part 50 (shown in fig. 2F).

In the examples disclosed herein, the polymer particles can be dispersed in a liquid carrier. The polymer particles can have several different morphologies. For example, the polymer particles may be of a polymer containing a high T dispersed with each other according to IPN (interpenetrating network)_gHydrophilic (hard) component and/or low T_gIndependent spherical particles of a polymer composition of a hydrophobic (soft) component, although a high T is expected_gHydrophilicity and T_gThe hydrophobic components may be otherwise mutually dispersed. For another example, the polymer particles may be formed of a high T that is continuous or discontinuous_gHydrophilic shell surrounded low T_gA hydrophobic core. For another example, the polymer particle morphology can be similar to raspberry, with low T_gA hydrophobic core is attached to the core by a plurality of smaller high Ts_gHydrophilic particles are surrounded. For yet another example, the polymer particles may comprise 2, 3, or 4 particles at least partially attached to each other.

In the examples herein, high T_gHydrophilic component/shell/particle and low T_gHydrophilic components/cores/particles may be defined with respect to each other (i.e. high T)_gThe hydrophilic component/shell/particle has a higher than low T_gT of hydrophilic component/core/particle_gAnd low T_gHydrophilic component/core/particle having less than high T_gT of hydrophilic component/shell/particle_g). In some examples, high T_gThe hydrophilic component/shell/particle has a T above 25 DEG C_g. In other examples, high T_gThe hydrophilic component/shell/particle has a T above 45 DEG C_g. In some examples, low T_gThe hydrophilic component/core/particle has a T below 25 DEG C_g. In other examples, low T_gThe hydrophilic component/core/particle has a T below 5 DEG C_g。

The polymer particles can be any latex polymer (i.e., a polymer capable of being dispersed in an aqueous medium) that is jettable via inkjet printing (e.g., thermal inkjet printing or piezoelectric inkjet printing). In some examples disclosed herein, the polymer particles are heteropolymers or copolymers. The heteropolymer may comprise a more hydrophobic component and a more hydrophilic component. In these examples, the hydrophilic component allows the particles to disperse in binder fluid 36, while the hydrophobic component is capable of coalescing upon exposure to heat so as to temporarily bond the metal build material particles 16 together to form cured green part 42'.

Low T useful for forming hydrophobic components_gExamples of monomers include C4 to C8 alkyl acrylates or C4 to C8 alkyl methacrylates, styrene, substituted methyl styrene, polyol acrylates or methacrylates, vinyl monomers, vinyl esters, and the like. Some specific examples include methyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, isobornyl acrylate, isobornyl methacrylate, stearyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, ethoxylated nonylphenol methacrylate, and mixtures thereof, Cyclohexyl methacrylate, trimethylcyclohexyl methacrylate, t-butyl methacrylate, N-octyl methacrylate, tridecyl methacrylate, isodecyl acrylate, dimethyl maleate, dioctyl maleate, acetoacetoxyethyl methacrylate, diacetone acrylamide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, divinylbenzene, styrene, methylstyrene (e.g., alpha-methylstyrene, p-methylstyrene), vinyl chloride, vinylidene chloride, vinylbenzyl chloride, acrylonitrile, methacrylonitrile, N-vinylimidazole, N-vinylcarbazoleN-vinyl-caprolactam, combinations thereof, derivatives thereof, or mixtures thereof.

The heteropolymer may be formed from at least two of the monomers listed above, or from at least one of the monomers listed above and a high T_gHydrophilic monomers, such as acidic monomers. Examples of acidic monomers that can be polymerized in forming the polymer particles include acrylic acid, methacrylic acid, ethacrylic acid, dimethylacrylic acid, maleic anhydride, maleic acid, vinylsulfonate, cyanoacrylate, vinylacetic acid, allylacetic acid, ethylideneacetic acid, propylideneacetic acid, crotonic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, vinylbenzoic acid, N-vinylsuccinamic acid, mesaconic acid, methacryloylalanine, acryloylhydroxyglycine, sulfoethylmethacrylic acid, sulfopropylacrylic acid, styrenesulfonic acid, sulfoethylacrylic acid, 2-methacryloyloxymethyl-1-sulfonic acid, maleic acid, 3-methacryloxypropyl-1-sulfonic acid, 3- (vinyloxy) propane-1-sulfonic acid, vinylsulfonic acid, vinylsulfuric acid, 4-vinylphenylsulfuric acid, vinylphosphonic acid, vinylphosphoric acid, vinylbenzoic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, combinations thereof, derivatives thereof, or mixtures thereof. High T_gOther examples of hydrophilic monomers include acrylamide, methacrylamide, monohydroxylated monomers, monoethoxylated monomers, polyhydroxylated monomers, or polyethoxylated monomers.

In the heteropolymers disclosed herein, low T_gThe hydrophobic component comprises about 65% to about 100% of the polymer, the high T_gThe hydrophilic component comprises from about 0.1% to about 35% of the polymer.

In one example, the selected monomers polymerize to form the desired heteropolymer. Any suitable polymerization method may be employed. For example, the hydrophobic-hydrophilic polymer particles may be formed by any of a variety of techniques, such as: i) make high T_gAttachment of hydrophilic polymers to Low T_gOn the surface of a hydrophobic polymer, ii) reactingBy leading to a higher T_gCopolymerization of the ratio of hydrophilic external component or shell Low T_gHydrophobic monomers and high T_gHydrophilic monomer, iii) adding a high T to the end of the copolymerization process_gHydrophilic monomers (or excess high T)_gHydrophilic monomer) such that there is a higher concentration of copolymerized high T at or near the surface_gHydrophilic monomers, or iv) it is known in the art to generate a higher T relative to the internal components or core_gHydrophilic outer component or shell. These hydrophobic-hydrophilic polymer particles may be core-shell particles. However, it is to be understood that these techniques may also form polymer particles having other morphologies, as described herein.

The polymer particles may have a particle size jettable via thermal inkjet printing or piezoelectric printing or continuous inkjet printing. In one example, the polymer particles have a particle size of about 10nm to about 300 nm.

In some examples, the polymer particles have a glass transition temperature (T) greater than (e.g., >) ambient temperature_g). In other examples, the polymer particles have a glass transition temperature (T) much greater (e.g., >) than the ambient temperature_g) (i.e., at least 15 ℃ above ambient temperature). As used herein, "ambient temperature" may refer to room temperature (e.g., about 18 ℃ to about 22 ℃), or to the temperature of the environment in which the 3D printing method is performed. An example of the 3D printing ambient temperature may be about 40 ℃ to about 50 ℃. Glass transition temperature T of the bulk material (e.g., the more hydrophobic portion) of the polymer particles_gAnd may be from 25 c to about 125 c. In one example, the glass transition temperature T of the bulk material (e.g., the more hydrophobic portion) of the polymer particles_gAbout 40 c or higher. Glass transition temperature T of bulk material_gCan be any temperature that enables the polymer particles to be ink jet printed without becoming too soft at the printer operating temperature.

The polymer particles may have a melting point of about 125 ℃ to about 200 ℃. In one example, the polymer particles may have a melting point of about 160 ℃.

The weight average molecular weight of the polymer particles can be from about 5,000Mw to about 500,000 Mw. In some examples, the weight average molecular weight of the polymer particles is about 100,000Mw to about 500,000 Mw. In some other examples, the weight average molecular weight of the polymer particles is about 150,000Mw to 300,000 Mw.

The polymer particles may be present in the binder fluid 36 in an amount of about 2 wt% to about 30 wt%, or about 3 wt% to about 20 wt%, or about 5 wt% to about 15 wt% (based on the total weight of the binder fluid 36). In another example, the polymer particles may be present in the binder fluid 36 in an amount of about 20 vol% to about 40 vol% (based on the total volume% of the binder fluid 36). It is believed that these polymer particle loadings provide a balance between adhesive fluid 36 with jetting reliability and bonding efficiency.

In some examples, the binder fluid 36 includes a coalescing solvent in addition to the polymer particles. In these examples, the coalescing solvent plasticizes the polymer particles and enhances coalescence of the polymer particles when exposed to heat in order to temporarily bond the metallic build material particles 16 together to form the solidified green part 42'. In some examples, binder fluid 36 may be composed of polymer particles and coalescing solvent (without other components). In these examples, the liquid carrier consists of coalescing solvent (without other components), and the coalescing solvent constitutes the balance of the binder fluid 36.

In some examples, the coalescing solvent may be a lactone, such as 2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, and the like. In other examples, the coalescing solvent may be a glycol ether or glycol ether ester such as tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol mono-n-butyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, diethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-n-butyl ether acetate, and the like. In still other examples, the coalescing solvent may be a water-soluble polyol, such as 2-methyl-1, 3-propanediol and the like. In still other examples, the coalescing solvent may be a combination of any of the above examples. In still other examples, the coalescing solvent is selected from the group consisting of 2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol mono-n-butyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, diethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-n-butyl ether acetate, 2-methyl-1, 3-propanediol, and combinations thereof.

The coalescing solvent may be present in the binder fluid 36 in an amount of about 0.1 wt% to about 50 wt% (based on the total weight of the binder fluid 36). In some examples, a greater or lesser amount of coalescing solvent may be used, depending in part on the spray architecture of the applicator 24.

In one example, the polymer particles are present in the binder fluid in an amount of about 2 wt% to about 30 wt%, and the coalescing solvent is present in the binder fluid in an amount of about 0.1 wt% to about 50 wt%.

As described above, the adhesive fluid 36 comprises polymer particles and a liquid carrier. As used herein, "liquid carrier" may refer to a liquid fluid in which polymer particles are dispersed to form the binder fluid 36. A wide variety of liquid carriers, including aqueous and non-aqueous carriers, may be used for the adhesive fluid 36. In some cases, the liquid carrier consists of the principal solvent, free of other components. In other examples, the adhesive fluid 36 may contain other ingredients, depending in part on the applicator 24 to be used to dispense the adhesive fluid 36. Examples of other suitable binder fluid components include co-solvents, surfactants, anti-microbial agents, anti-coking agents, viscosity modifiers, pH adjusters, and/or sequestering agents. The presence of co-solvents and/or surfactants in binder fluid 36 may help to achieve a particular wetting behavior with metal build material 16.

The primary solvent may be water or a non-aqueous solvent (e.g., ethanol, acetone, N-methylpyrrolidone, aliphatic hydrocarbons, etc. in some examples, the adhesive fluid 36 is composed of polymer particles and a primary solvent (free of other components).

Classes of organic co-solvents that may be used in the water-based binder fluid 36 include aliphatic alcohols, aromatic alcohols, glycols, glycol ethers, polyglycol ethers, 2-pyrrolidone, caprolactam, formamide, acetamide, glycols, and long chain alcohols. Examples of such co-solvents include primary aliphatic alcohols, secondary aliphatic alcohols, 1, 2-alcohols, 1, 3-alcohols, 1, 5-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higher homologs of polyethylene glycol alkyl ethers (C6-C12), N-alkyl caprolactams, unsubstituted caprolactams, both substituted and unsubstituted formamides, both substituted and unsubstituted acetamides, and the like.

Examples of some suitable co-solvents include water-soluble high boiling solvents (i.e., humectants) that have a boiling point of at least 120 ℃ or higher. Some examples of high boiling solvents include 2-pyrrolidone (boiling point about 245 ℃), 2-methyl-1, 3-propanediol (boiling point about 212 ℃), and combinations thereof. The co-solvent may be present in the binder fluid 36 in a total amount of about 1 wt% to about 50 wt% of the total wt% of the binder fluid 36, depending on the jetting architecture of the applicator 24.

Surfactants may be used to improve the wettability and jettability of the adhesive fluid 36. Examples of suitable surfactants include self-emulsifying nonionic wetting agents based on acetylenic diol chemistry (e.g., from Air Products and Chemicals, inc

SEF), non-ionic fluorosurfactants (e.g., from DuPont)

Fluorosurfactants, previously known as ZONYL FSO) and combinations thereof. In other examples, the surfactant is an ethoxylated low foam wetting agent (e.g., from Air Products and Chemical inc

440 or

CT-111) or ethoxylated wetting agents and molecular defoamers (e.g., from Air Products and Chemical inc

420). Still other suitable surfactants include nonionic wetting agents and molecular defoamers (e.g., from Air Products and chemical inc

104E) Or water-soluble nonionic surfactants (e.g., TERGITOL from The Dow Chemical Company)^TMTMN-6 or TERGITOL^TM15-S-7). In some instances, it may be desirable to use a surfactant having a hydrophilic-lipophilic balance (HLB) of less than 10.

Whether a single surfactant or a combination of surfactants is used, the total amount of surfactant in the binder fluid 36 may be from about 0.01 wt% to about 10 wt% of the total wt% of the binder fluid 36. In another example, the total amount of surfactant in the binder fluid 36 may be about 0.5 wt% to about 2.5 wt% of the total wt% of the binder fluid 36.

The liquid carrier may also comprise an antimicrobial agent. Suitable antimicrobial agents include biocides and fungicides. Exemplary antimicrobial agents may include NUOSEPT^TM(Troy Corp.)、UCARCIDE^TM(Dow Chemical Co.)、

M20(Thor) and combinations thereof. Examples of suitable biocides include aqueous solutions of 1, 2-benzisothiazolin-3-one (e.g., from Arch Chemicals, inc

GXL), quaternary ammonium compounds (e.g.

2250 and 2280,

50-65B and

250-T, both from Lonza Ltd. Corp.) and methylisothiazolone in water (e.g. from Dow Chemical Co., Ltd.)

MLX). The biocide or antimicrobial agent may be added in any amount from about 0.05 wt% to about 0.5 wt% relative to the total wt% of the binder fluid 36 (as indicated by regulatory usage levels).

An anti-coking agent may be included in the binder fluid 36. Coking refers to the deposition of dry ink (e.g., binder fluid 36) on the heating elements of a thermal inkjet printhead. Anti-coking agents are included to help prevent the accumulation of coke. Examples of suitable anti-coking agents include oleyl polyether-3-phosphate (e.g., as Crodafos)^TMO3A or Crodafos^TMN-3 acids available from Croda), or a combination of oleylpolyether-3-phosphate and low molecular weight (e.g., < 5,000) polyacrylic acid polymers (e.g., as CARBOSPERSE)^TMK-7028 Polyacrylate was purchased from Lubrizol). Whether a single anti-coking agent or a combination of anti-coking agents is used, the total amount of anti-coking agent in the binder fluid 36 may be greater than 0.20 wt% to about 0.62 wt% of the total wt% of the binder fluid 36. In one example, oleylpolyether-3-phosphate is included in an amount of about 0.20 wt% to about 0.60 wt%, and the low molecular weight polyacrylic polymer is included in an amount of about 0.005 wt% to about 0.03 wt%.

Sequestering agents such as EDTA (ethylenediaminetetraacetic acid) may be included to eliminate the deleterious effects of heavy metal impurities, and buffer solutions may be used to control the pH of the binder fluid 36. Each of these components may be used, for example, in an amount of 0.01 to 2% by weight. Viscosity modifiers and buffers may also be present, as well as other additives known to those skilled in the art to modify the properties of the binder fluid 36 as desired. Such additives may be present in an amount of about 0.01 wt% to about 20 wt%.

The applicator 24 may scan across the build area platform 12 in the direction indicated by arrow 26, e.g., along the y-axis. The applicator 24 may be, for example, an inkjet applicator, such as a thermal inkjet printhead, a piezoelectric printhead, or the like, and may extend the width of the build area platform 12. Although the applicator 24 is shown in fig. 1 as a single applicator, it is to be understood that the applicator 24 may comprise multiple applicators spanning the width of the build area platform 12. Further, the applicators 24 may be positioned in multiple print bars. The applicator 24 may also be scanned along the x-axis, for example in a configuration in which the applicator 24 does not span the width of the build area platform 12 to enable the applicator 24 to deposit adhesive fluid 36 over a large area of the layer of metallic build material 16. The applicator 24 may thus be connected to a moving XY table or translating carriage (neither shown) that moves the applicator 24 adjacent to the build area platform 12 to deposit the adhesive fluid 36 in a predetermined area of the layer of metallic build material 16 that has been formed on the build area platform 12 according to the methods disclosed herein. The applicator 24 may include a plurality of nozzles (not shown) through which the adhesive fluid 36 is sprayed.

The applicator 24 may deliver droplets of the adhesive fluid 36 at a resolution of about 300 Dots Per Inch (DPI) to about 1200 DPI. In other examples, the applicator 24 may deliver droplets of the adhesive fluid 36 with greater or lesser resolution. The drop velocity can be about 2m/s to about 24m/s and the firing frequency can be about 1kHz to about 100 kHz. In one example, each droplet may be in the order of about 10 picoliters (pl) per droplet, although it is contemplated that higher or lower droplet sizes may be used. For example, the droplet size may be about 1pl to about 400 pl. In some examples, the applicator 24 is capable of delivering variable sized droplets of the adhesive fluid 36.

Each of the foregoing physical elements may be operatively connected to a controller 28 of printing system 10. Controller 28 may control the operation of build area platform 12, build material supply 14, build material distributor 18, and applicator 24. As one example, controller 28 may control actuators (not shown) to control various operations of the components of 3D printing system 10. Controller 28 may be a computing device, a semiconductor-based microprocessor, a Central Processing Unit (CPU), an Application Specific Integrated Circuit (ASIC), and/or another hardware device. Although not shown, the controller 28 may be connected to the 3D printing system 10 components via communication lines.

The controller 28 manipulates and transforms data, which may be represented as physical (electronic) quantities in registers and memory of the printer, in order to control the physical elements to generate the 3D part 50. Thus, controller 28 is depicted as being in communication with data bins 30. The data bin 30 may include data regarding a 3D part 50 to be printed by the 3D printing system 10. Data for selective delivery of the metallic build material particles 16, the binder fluid 36, and so forth may be derived from a model of the 3D part 50 to be formed. For example, the data may include the locations on the various layers of the metallic build material particles 16 where the applicator 24 is to deposit the binder fluid 36. In one example, the controller 28 can use this data to control the applicator 24 to selectively apply the adhesive fluid 36. Data bin 30 may also include machine-readable instructions (stored on a non-transitory computer-readable medium) to cause controller 28 to control the amount of metallic build material particles 16 supplied by build material supply 14, movement of build area platform 12, movement of build material distributor 18, movement of applicator 24, and so forth.

As shown in fig. 1, printing system 10 may also include heaters 32, 32'. In some examples, heater 32 comprises a conventional oven or oven, a microwave oven, or a device capable of hybrid heating (i.e., conventional heating and microwave heating). This type of heater 32 can be used to heat the entire build material cake 44 after printing is complete (see fig. 2E), or to heat the cured green part 42 ', or to heat the at least substantially polymer-free gray part 48 after removing the cured green part 42' from the build material cake 44 (see fig. 2F). In some examples, patterning may be performed in printing system 10, and then build material platform 12 with patterned green part 42 thereon may be disengaged from system 10 and placed into heater 32 for each heating stage. In other examples, the heater 32 may be a conductive heater or a radiant heater (e.g., an infrared lamp) integrated into the system 10. These other types of heaters 32 may be placed below the build area platform 12 (e.g., conductive heating from below the platform 12), or may be placed above the build area platform 12 (e.g., radiant heating of the surface of the layer of build material). Combinations of these types of heating may also be used. These other types of heaters 32 may be used throughout the 3D printing process. In still other examples, the heater 32' may be a radiant heat source (e.g., a curing lamp) positioned to heat the various layers 34 after the adhesive fluid 36 has been applied to the various layers 34 (see fig. 2C). In the example shown in fig. 1, a heater 32' is connected to the side of the applicator 24, which allows printing and heating to occur in a single pass. In some examples, both heaters 32 and 32' may be used.

Referring now to fig. 2A to 2F, one example of a 3D printing method is depicted. Prior to performing method 100 or as part of method 100, controller 28 may access data stored in data store 30 relating to 3D part 50 to be printed. The controller 28 can determine the number of layers of metallic build material particles 16 to be formed and the location at which the binder fluid 36 is to be deposited from the applicator 24 onto each respective layer.

As shown in fig. 2A and 2B, method 100 includes applying a metallic build material 16. In FIG. 2A, build material supply 14 may supply metallic build material particles 16 to a location such that they are ready to be spread onto build area platform 12. In FIG. 2B, a build material distributor 18 may spread supplied metallic build material particles 16 onto the build area platform 12. Controller 28 may execute control build material supply instructions to control build material supply 14 to properly position metallic build material particles 16 and may execute control spreader instructions to control build material distributor 18 to spread the supplied metallic build material particles 16 over build area platform 12 to thereby form layer 34 of metallic build material particles 16 thereon. As shown in FIG. 2B, a layer 34 of metallic build material particles 16 has been applied.

Layer 34 has a substantially uniform thickness across build area platform 12. In one example, layer 34 is about 30 μm to about 300 μm thick, although thinner or thicker layers may also be used. For example, the thickness of layer 34 may be about 20 μm to about 500 μm. For finer feature definition, the minimum layer thickness may be about 2x particle size (as shown in fig. 2B). In some examples, the layer thickness may be about 1.2 x (i.e., 1.2 times) the particle size.

Referring now to FIG. 2C, method 100 continues by selectively applying adhesive fluid 36 on portion 38 of metal build material 16. As shown in fig. 2C, an adhesive fluid 36 can be dispensed by the applicator 24. The applicator 24 may be a thermal inkjet printhead, a piezoelectric printhead, or the like, and selective application of the adhesive fluid 36 may be achieved by an associated inkjet printing technique. Thus, selective application of the binder fluid 36 may be achieved by thermal inkjet printing or piezoelectric inkjet printing.

Controller 28 may execute instructions to control applicator 24 (e.g., in the direction indicated by arrow 26) to deposit binder fluid 36 onto predetermined portions 38 of metal build material 16 that are to be part of patterned green part 42 and that are to be finally sintered to form 3D part 50. Applicator 24 may be programmed to receive commands from controller 28 and deposit adhesive fluid 36 according to the cross-sectional pattern of the layer of 3D part 50 to be formed. As used herein, the cross-section of the layer of the 3D part 50 to be formed refers to a cross-section parallel to the surface of the build area platform 12. In the example shown in fig. 2C, applicator 24 selectively applies adhesive fluid 36 on those portions 38 that are to be fused to become the first layer of 3D part 50. As one example, if the shape of the 3D part to be formed resembles a cube or cylinder, the binder fluid 36 will be deposited on at least a portion of the layer 34 of metal build material particles 16 in a square pattern or a circular pattern (as viewed from the top), respectively. In the example shown in fig. 2C, adhesive fluid 36 is deposited in a square pattern on portion 38 of layer 34, and not on portion 40.

As described above, the adhesive fluid 36 comprises polymer particles and a liquid carrier. As also described above, in some examples, the binder fluid 36 also includes a coalescing solvent (as or in addition to the liquid carrier). It is to be understood that a single adhesive fluid 36 may be selectively applied to pattern layer 34, or multiple adhesive fluids 36 may be selectively applied to pattern layer 34.

Although not shown, the method 100 may include preparing the adhesive fluid 36 prior to selectively applying the adhesive fluid 36. Preparing the adhesive fluid 36 may include preparing polymer particles and then adding the polymer particles to the liquid carrier.

When each polymer particle contains a low T_gHydrophobic component and high T_gWhere hydrophilic components are present, the polymer particles may be prepared by any suitable method. As an example, the polymer particles may be prepared by one of the following methods.

In one example, each polymer particle can be made low in T by polymerization_gHydrophobic monomers to form low T_gHydrophobic component, polymeric high T_gHydrophilic monomers to form high T_gHydrophilic component and high T_gAttachment of hydrophilic component to Low T_gOn the surface of the hydrophobic component.

In another example, each polymer particle may pass through a low T of from 5:95 to 30:70_gHydrophobic monomer pair high T_gRatio polymerization of hydrophilic monomers Low T_gHydrophobic monomers and high T_gHydrophilic monomers. In this example, the soft low T_gThe hydrophobic monomer can be dissolved in the hard high T_gHydrophilic monomers.

In yet another example, each polymer particle can be made by using a low T_gThe hydrophobic monomer begins the polymerization process, followed by the addition of high T_gHydrophilic monomers and then ending the polymerization process. In this example, the polymerization process may be at a low T_gHigher concentration of high T at or near the surface of hydrophobic component_gThe hydrophilic monomer is polymerized.

In yet another example, each polymer particle can be made by using a low T_gHydrophobic monomers and high T_gThe hydrophilic monomer begins the copolymerization process, followed by the addition of an additional high T_gHydrophilic monomers and then ending the copolymerization process. In this example, the copolymerization process can be at a low T_gHigher concentration of high T at or near the surface of the hydrophobic component_gAnd (3) copolymerizing the hydrophilic monomer.

Low T used in any of these examples_gHydrophobic monomers and/or high T_gThe hydrophilic monomer may be (respectively) any of the low T's listed above_gHydrophobic monomers and/or high T_gA hydrophilic monomer. In one example, low T_gThe hydrophobic monomer is selected from the group consisting of C4 to C8 alkyl acrylate monomers, C4 to C8 alkyl methacrylate monomers, styrene monomers, substituted methylstyrene monomers, vinyl ester monomers, and combinations thereof; high T_gThe hydrophilic monomer is selected from the group consisting of acidic monomers, unsubstituted amide monomers, alcohol acrylate monomers, alcohol methacrylate monomers, C1 to C2 alkyl acrylate monomers, C1 to C2 alkyl methacrylate monomers, and combinations thereof.

The resulting polymer particles may exhibit a core-shell structure, a mixed or interlaced polymer structure, or some other morphology.

When the binder fluid 36 is selectively applied in the desired portion 38, the polymer particles (present in the binder fluid 36) infiltrate the inter-particle spaces among the metallic build material particles 16. The volume of adhesive fluid 36 applied per unit of metal build material 16 in patterned portion 38 may be sufficient to fill a major portion, or a majority, of the porosity present in the thickness of portion 38 of layer 34.

It is to be understood that the portion 40 of the metal build material 16 to which the binder fluid 36 is not applied also does not have polymer particles introduced thereto. Thus, these portions do not become part of the finally formed patterned green part 42.

The process shown in fig. 2A-2C may be repeated to iteratively build multiple patterned layers and form patterned green body elements 42 (see fig. 2E).

Fig. 2D shows the initial formation of a second layer of metal build material 16 on layer 34 patterned with binder fluid 36. In fig. 2D, after depositing adhesive fluid 36 onto predetermined portion 38 of layer 34 of metal build material 16, controller 28 may execute instructions to move build area platform 12 a relatively small distance in the direction indicated by arrow 20. In other words, build area platform 12 may be lowered to enable the formation of the next layer of metal build material 16. For example, build material platform 12 may be lowered a distance equivalent to the height of layer 34. Further, after lowering build area platform 12, controller 28 may control build material supply 14 to supply additional metallic build material 16 (e.g., by operating an elevator, screw conveyor, or the like), and control build material distributor 18 to form another layer of metallic build material particles 16 with additional metallic build material 16 on top of previously formed layer 34. The newly formed layer may be patterned with binder fluid 36.

Referring back to fig. 2C, in another example of the method 100, the layer 34 may be exposed to heat using the heater 32' after the adhesive fluid 36 is applied to the layer 34 and before another layer is formed. The heater 32' may be used to activate the binder fluid 36 during the layer-by-layer printing process and produce a layer of stabilized and cured green part. Heating to form the cured green part layer may be performed at a temperature that activates (or cures) the binder fluid 36, but does not melt or sinter the metal build material 16. In one example, the activation temperature is near the melting point of the polymer particles. Other examples of suitable activation temperatures are provided below. In this example, the process shown in fig. 2A-2C (including heating layer 34) may be repeated to iteratively build multiple cured layers and produce a cured green part 42'. The cured green part 42' may then be exposed to the process described with reference to fig. 2F.

As shown in fig. 2E, repeated formation and patterning of new layers (without curing the individual layers) results in the formation of a build material cake 44 that includes patterned green part 42 that resides in non-patterned portions 40 of individual layers 34 of metal build material 16. Patterned green part 42 is a volume of build material cake 44 filled with metallic build material 16 and binder fluid 36 within the inter-particle spaces. The remainder of the build material cake 44 is composed of the non-patterned metal build material 16.

As also shown in fig. 2E, the construction material cake 44 can be exposed to heat or radiation as indicated by arrow 46 to generate heat. The applied heat may be sufficient to activate the binder fluid 36 in the patterned green part 42 and produce a stabilized and cured green part 42'. In one example, heat source 32 may be used to apply heat to build material cake 44. In the example shown in fig. 2E, a cake of build material 44 can remain on the build area platform 12 while being heated by the heat source 32. In another example, the build area platform 12 on which the cake of build material 44 is placed may be disengaged from the applicator 24 and placed in the heat source 32. Any of the aforementioned heat sources 32 and/or 32' may be used.

The activation/curing temperature may depend in part on one or more of the following: t of polymer particles_gThe melt viscosity of the polymer particles and/or whether and what coalescing solvent to use. In one example, heating to form the cured green part 42' may be performed at a temperature that is capable of activating (or curing) the binder fluid 36, but not sintering the metal build material 16 or thermally degrading the polymer particles of the binder fluid 36. In one example, the activation temperature is near the melting point of the bulk material of the polymer particles of the binder fluid 36 and below the thermal decomposition temperature of the polymer particles (i.e., below the temperature threshold at which thermal decomposition occurs). For most suitable latex-based polymer particles, the upper limit of the activation/curing temperature is from about 250 ℃ to about 270 ℃. Above this temperature threshold, the polymer particles will chemically degrade into volatile species and leave patterned green part 42, thereby ceasing to function. In other examples, the binder fluid 36 activation temperature may be above the melting point of the polymer particles. As one example, the adhesive fluid activation temperature may be from about 50 ℃ to about 200 ℃. As another example, the adhesive fluid activation temperature may be from about 100 ℃ to about 200 ℃. As yet another example, the adhesive fluid activation temperature may be from about 80 ℃ to about 200 ℃. As yet another example, the adhesive fluid activation temperature may be about 90 ℃.

The length of time that heat 46 is applied and the rate at which green part 42 is thermoplastically patterned may depend on, for example, one or more of the following: characteristics of the heat or radiation source 32, 32', characteristics of the polymer particles, characteristics of the metal build material 16 (e.g., metal type, particle size, etc.), and/or characteristics of the 3D part 50 (e.g., wall thickness). The patterned green part 42 can be heated at the binder fluid activation temperature for an activation/curing period of time of from about 1 minute to about 360 minutes. In one example, the activation/curing time period is 30 minutes. In another example, the activation/curing time period may be from about 2 minutes to about 240 minutes. Patterned green part 42 can be heated to the adhesive fluid activation temperature at a rate of about 1 c/min to about 10 c/min, although slower or faster heating rates are contemplated. The heating rate may depend in part on one or more of the following: the adhesive fluid 36 used, the dimensions (i.e., thickness and/or area (across the x-y plane)) of the layer 34 of the metallic build material 16, and/or the characteristics (e.g., dimensions, wall thickness, etc.) of the 3D part 50. In one example, patterned green part 42 is heated to the adhesive fluid activation temperature at a rate of about 2.25 ℃/minute.

Heating to near the melting point of the polymer particles causes the polymer particles to coalesce into a continuous polymer phase in the metallic build material particles 16 of the patterned green part 42. As described above, the coalescing solvent (when included in the binder fluid 36) plasticizes the polymer particles and enhances coalescence of the polymer particles. The continuous polymer phase may act as a heat-activated adhesive between the metallic build material particles 16 to form a stabilized cured green part 42'.

Heating to form the cured green part 42' may also cause a significant portion of the fluid to evaporate from the patterned green part 42. The vaporized fluid may comprise any binder fluid component. Fluid evaporation may result in some densification of the cured green part 42' by capillary action.

The stabilized cured green part 42' exhibits handleable mechanical durability.

The cured green part 42' may then be extracted from the cake of build material 44. The cured green part 42' may be extracted by any suitable means. In one example, the cured green part 42 'may be extracted by lifting the cured green part 42' from the unpatterned metallic build material particles 16. Extraction tools, including pistons and springs, may be used.

As the cured green part 42 'is extracted from the cake of build material 44, the cured green part 42' may be removed from the build area platform 12 and placed in a heating mechanism. The heating mechanism may be a heater 32.

In some examples, the cured green part 42' may be cleaned to remove unpatterned metallic build material particles 16 from its surface. In one example, the cured green part 42' may be cleaned with a brush and/or an air jet.

As shown in fig. 2F, after extraction and/or cleaning of the cured green part 42 ', the cured green part 42' may be heated to remove activated polymer particles (which have coalesced into a continuous polymer phase) to produce an at least substantially polymer-free gray part 48. In other words, green part 42' can be heat cured to remove the continuous polymer phase. As also shown in fig. 2F, the at least substantially polymer-free ash blank component 48 may then be sintered to form a final 3D component 50. The thermal debinding and the thermal sintering occur at two different temperatures, wherein the temperature for debinding is lower than the temperature for sintering. The debinding and sintering heating stage is generally depicted in fig. 2F, where heating or radiation to generate heat may be applied by the heat source 32 as indicated by arrows 46.

Heating debonding is achieved at a thermal decomposition temperature sufficient to thermally decompose the continuous polymer phase. Thus, the temperature for de-binding depends on the material of the polymer particles of the binder fluid 36. In one example, the thermal decomposition temperature is about 250 ℃ to about 600 ℃. In another example, the thermal decomposition temperature is from about 280 ℃ to about 600 ℃, or to about 500 ℃. The continuous polymer phase may have a clean thermal decomposition mechanism (e.g., leaving a solid residue of < 5 wt% of the initial binder, in some cases < 1 wt% of the initial binder). A smaller residue percentage (e.g., near 0%) is more desirable. During the de-binding stage, the long chains of the continuous polymer phase are first broken down into shorter molecular fragments, which are converted into a liquid phase of lower viscosity. The capillary pressure generated during this liquid evaporation draws the metal build material particles 16 together, resulting in further densification and formation of an at least substantially polymer-free ash component 48.

While not being bound by any theory, it is believed that the at least substantially polymer-free gray part 48 can retain its shape because of, for example, one or more of the following: i) the at least substantially polymer-free gray part 48 experiences a low amount of stress due to its lack of physical treatment, ii) a low level of necking between the metal build material particles 16 at the thermal decomposition temperature of the polymer particles, and/or iii) capillary forces generated by the removal of the continuous polymer phase that push the metal build material particles 16 together. The at least substantially polymer-free ash blank component 48 can retain its shape despite the at least substantial removal of the continuous polymer phase and the metal build material particles 16 not yet sintered. Heating to form the substantially polymer-free ash blank component 48 may begin an initial stage of sintering, which may result in the formation of a weak bond that is strengthened during the final sintering process.

The heat sintering is achieved at a sintering temperature sufficient to sinter the remaining metallic build material particles 16. The sintering temperature is highly dependent on the composition of the metallic build material particles 16. During the heating/sintering process, the at least substantially polymer-free ash blank component 48 may be heated to a temperature that is about 80% to about 99.9% of the melting point or solidus temperature, eutectic temperature, or peritectic temperature of the metallic build material 16. In another example, the at least substantially polymer-free ash blank component 48 can be heated to a temperature that is about 90% to about 95% of the melting point or solidus temperature, eutectic temperature, or peritectic temperature of the metallic build material 16. In yet another example, the at least substantially polymer-free ash blank component 48 can be heated to a temperature that is about 60% to about 85% of the melting point or solidus temperature, eutectic temperature, or peritectic temperature of the metallic build material 16. The sintering heating temperature may also depend on the particle size and sintering time (i.e., high temperature exposure time). As an example, the sintering temperature may be about 850 ℃ to about 1400 ℃. In another example, the sintering temperature is at least 900 ℃. One example of a sintering temperature for bronze is about 850 deg.c and one example of a sintering temperature for stainless steel is about 1300 deg.c. While these temperatures are provided as examples of sintering temperatures, it is understood that the sintering heating temperature is dependent on the metal build material 16 employed and may be higher or lower than the examples provided. The sintered and fused metal build material particles 16 are heated at a suitable temperature to form a completed 3D part 50 that may be densified even further relative to the at least substantially polymer-free ash blank part 48. For example, as a result of sintering, the density may vary from a density of 50% to over 90%, in some cases very close to 100% of theoretical density.

The length of time that heat 46 (for each debinding and sintering) is applied and the rate at which heating elements 42', 48 are applied may depend on, for example, one or more of the following: characteristics of heat or radiation source 32, characteristics of polymer particles, characteristics of metal build material 16 (e.g., metal type, particle size, etc.), and/or characteristics of 3D part 50 (e.g., wall thickness).

The cured green part 42' may be heated at the thermal decomposition temperature for a thermal decomposition period of about 10 minutes to about 72 hours. In one example, the thermal decomposition time period is 60 minutes. In another example, the thermal decomposition time period is 180 minutes. The cured green part 42' can be heated to the thermal decomposition temperature at a rate of about 0.5 deg.c/minute to about 20 deg.c/minute. The heating rate may depend in part on one or more of the following: an amount of continuous polymer phase in the cured green part 42 ', a porosity of the cured green part 42 ', and/or characteristics (e.g., size, wall thickness, etc.) of the cured green part 42 '/3D part 50.

The at least substantially polymer-free gray blank component 48 can be heated at the sintering temperature for a sintering time period ranging from about 20 minutes to about 15 hours. In one example, the sintering time period is 240 minutes. In another example, the sintering time period is 360 minutes. The at least substantially polymer-free ash blank component 48 can be heated to the sintering temperature at a rate of from about 1 deg.c/minute to about 20 deg.c/minute. In one example, the at least substantially polymer-free ash blank component 48 is heated to the sintering temperature at a rate of from about 10 ℃/minute to about 20 ℃/minute. To produce a more favorable grain structure or microstructure, a high rate of rise in temperature to the sintering temperature may be desirable. However, in some cases, a slower ramp rate may be desirable. Thus, in another example, the at least substantially polymer-free ash blank component 48 is heated to the sintering temperature at a rate of from about 1 ℃/minute to about 3 ℃/minute. In yet another example, the at least substantially polymer-free ash blank component 48 is heated to the sintering temperature at a rate of about 1.2 ℃/minute. In yet another example, the at least substantially polymer-free ash blank component 48 is heated to the sintering temperature at a rate of about 2.5 ℃/minute.

In an example of the method 100: heating the cured green part 42' to a thermal decomposition temperature for a thermal decomposition time period of from about 30 minutes to about 72 hours; the at least substantially polymer-free gray blank component 48 is heated to the sintering temperature for a sintering time period of from about 20 minutes to about 15 hours. In another example of the method 100: heating the cured green part 42' to the thermal decomposition temperature is achieved at a rate of about 0.5 ℃/minute to about 10 ℃/minute; and heating the at least substantially polymer-free ash blank component 48 to the sintering temperature is accomplished at a rate of from about 1 deg.c/minute to about 20 deg.c/minute.

In some examples of the method 100, the heat 46 (for each of debinding and sintering) is applied in an environment containing an inert gas, a low reactivity gas, a reducing gas, or a combination thereof. In other words, heating the cured green body component 42' to the thermal decomposition temperature and heating the at least substantially polymer-free ash body component 48 to the sintering temperature is achieved in an environment containing an inert gas, a low reactivity gas, a reducing gas, or a combination thereof. De-binding may be achieved in an environment containing an inert gas, a low reactivity gas, and/or a reducing gas to thermally decompose the continuous polymer phase rather than undergoing an alternative reaction that fails to produce an at least substantially polymer-free grey cast part 48 and/or prevents oxidation of metal build material 16. Sintering may be accomplished in an environment containing inert, low reactivity, and/or reducing gases to sinter metal build material 16 rather than undergoing an alternative reaction (e.g., an oxidation reaction) that fails to produce metallic 3D part 50. Examples of inert gases include argon, helium, and the like. Examples of the low reactivity gas include nitrogen gas, and examples of the reducing gas include hydrogen gas, carbon monoxide gas, and the like.

In other examples of the method 100, the heat 46 (for each of debinding (i.e., heating the cured green body 42' to a thermal decomposition temperature) and sintering (i.e., heating the at least substantially polymer-free soot body part to a sintering temperature)) is applied in an environment containing carbon in addition to an inert gas, a low reactivity gas, a reducing gas, or a combination thereof. Debinding and sintering may be accomplished in an environment containing carbon to reduce the partial pressure of oxygen in the environment and further prevent oxidation of the metal build material 16 during debinding and sintering. One example of carbon that can be placed in a heated environment includes graphite rods. In other examples, a graphite furnace may be used.

In still other examples of the method 100, the heat 46 (for each debinding and sintering) is applied in a low pressure or vacuum environment. Debinding and sintering may be accomplished in a low pressure or vacuum environment to thermally decompose the continuous polymer phase and/or prevent oxidation of the metallic build material 16. In addition, sintering at low pressures or under vacuum may allow for more complete and faster pore collapse, thereby resulting in higher density parts. However, when the metal build material 16 (e.g., Cr) is able to evaporate under such conditions, vacuum cannot be used during sintering. In one example, the low pressure environment is at about 1E-5 Torr (1X 10)^-5Torr) to a pressure of about 10 torr.

Although not shown, the operations depicted in fig. 2E and 2F may be automated, and controller 28 may control the operations.

One example of a 3D printing method 200 is depicted in fig. 5. It is to be understood that an example of the method 200 shown in fig. 5 is discussed in detail herein (e.g., in fig. 2A-2F and text corresponding thereto).

As shown at reference numeral 202, the method 200 includes applying a metallic build material 16.

As shown at reference numeral 204, the method 200 further includes selectively applying an adhesive fluid 36 over at least a portion 38 of the metal build material 16, the adhesive fluid 36 including a liquid carrier and polymer particles dispersed in the liquid carrier.

As shown at reference numeral 206, method 200 further includes repeating the application of metallic build material 16 and the selective application of binder fluid 36 to create patterned green part 42.

As shown at reference numeral 208, the method 200 further includes heating the patterned green part 42 to near the melting point of the polymer particles, thereby activating the binder fluid 36 and producing a cured green part 42'.

As shown at reference numeral 210, the method 200 further includes heating the cured green part 42' to a thermal decomposition temperature of the polymer particles, thereby producing an at least substantially polymer-free gray part 48.

As shown at reference numeral 212, the method 200 further includes heating the at least substantially polymer-free soot body component 48 to a sintering temperature to form the metal component 50.

In one example of the method 200: the polymer particles have a glass transition temperature of about 25 ℃ to about 125 ℃; melting point of about 125 ℃ to about 200 ℃; a thermal decomposition temperature of from about 250 ℃ to about 600 ℃; the sintering temperature is about 850 ℃ to about 1400 ℃.

In another example of the method 200: applying a metallic build material 16 on the build area platform 12, selectively applying a binder fluid 36, repeating the applying and selectively applying, heating the patterned green part 42 to near the melting point; and after heating patterned green part 42 to about the melting point, the method further comprises: removing the cured green part 42' from the build area platform 12; and the cured green part is placed in the heating mechanism 36.

In yet another example of the method 200: the metallic build material is a powder having an average particle size of about 5 μm to about 200 μm; upon heating to a sintering temperature, the metallic build material sinters into a continuum to form a metallic component; and the sintering temperature is less than a melting point, solidus temperature, eutectic temperature, or peritectic temperature of the metallic build material.

To further illustrate the disclosure, examples are given herein. It is to be understood that these examples are provided for illustrative purposes and are not to be construed as limiting the scope of the present disclosure.

Examples

Example 1

Example 3D metal parts (referred to as "example part 1") were printed. The metal build material used to print example part 1 was spherical bronze (90 wt% Cu and 10 wt% Sn) powder with a D50 of 32 μm (i.e. median particle size distribution with population 1/2 above this value and 1/2 below this value). The binder fluid used for printing example part 1 contained an acrylic binder latex dispersion as the polymer particles, 2-methyl-1, 3-propanediol and 2-pyrrolidone as the coalescing solvent. The general formulation of the binder fluid used for printing example part 1 is shown in table 1 with the wt% of each component used. The weight percent of acrylic adhesive latex dispersion represents% actives, i.e., all acrylic adhesive latex solids present in the final formulation.

TABLE 1

Example part 1 was printed by applying a layer of bronze powder and binder fluid to form a patterned green part in the form of a gear. The thickness of each layer is about 100 μm. The patterned green part was cured by heating the entire powder bed and build material cake in an oven. The patterned green part was heated from room temperature to 180 ℃ at a rate of 2.25 ℃/min and held at 180 ℃ for 30 minutes. The cured green part was easily extracted from the unpatterned bronze powder and cleaned with a brush and air jet. The cured green part after breaking free the cake is shown in fig. 3A.

Subsequently, the cured green part was placed in a tube furnace (MT1 Corp. OTF-1200X-S) on an elevated alumina supportUL) so as to flow at a rate of about 14 cc/min at room temperature and atmospheric pressure, a gas mixture of nitrogen and hydrogen (96% N)₂And 4% of H₂) So that there is a good air flow around the cured green part. The cured green part was heated from 180 ℃ to 300 ℃ at a rate of 0.5 ℃/minute and held at 300 ℃ for 60 minutes to ensure complete burn-out of the polymer particles and produce an at least substantially polymer-free grey part. The at least substantially polymer-free soot body part was heated from 300 ℃ to 850 ℃ at a rate of 1.2 ℃/minute and held at 850 ℃ for 360 minutes to sinter the at least substantially polymer-free soot body part and produce example part 1. Example part 1 was cooled from 850 ℃ to room temperature at a rate of 5 ℃/min.

Example part 1 is shown in fig. 3B. The density of example part 1 was measured by gas pycnometer method and found to be 8.63g/cm³It is 8.7g/cm³98% of the bulk density.

Example 2

Another example 3D metal part (referred to as "example part 2") was printed. The metallic build material used for printing example part 2 was a spherical stainless steel (316L) powder with a D50 of 42 μm (i.e., median of particle size distribution with population 1/2 above this value and 1/2 below this value). The binder fluid used for printing example part 2 was the binder fluid described in example 1.

Example part 2 was printed by applying a layer of stainless steel powder and binder fluid to form a patterned green part in the form of a gear. The thickness of each layer is about 100 μm. The patterned green part was cured by heating the entire powder bed and build material cake in an oven. The patterned green part was heated from room temperature to 180 ℃ at a rate of 2.25 ℃/min and held at 180 ℃ for 30 minutes. The cured green part was easily extracted from the unpatterned stainless steel powder and cleaned with a brush and air jet. The cured green part after breaking free the cake is shown in fig. 4A.

Subsequently, the cured green part was placed in a tube furnace (MT1 Corp) on an elevated alumina supportGSL-1600X-50-UL) to flow a gas mixture of nitrogen and hydrogen (96% N) at a rate of about 14 cc/min at room temperature and atmospheric pressure₂And 4% of H₂) So that there is a good air flow around the cured green part. Graphite rods were placed adjacent to the cured green part to reduce the oxygen partial pressure in the furnace during binder removal and sintering. The cured green part was heated from 238 ℃ to 300 ℃ at a rate of 0.5 ℃/minute and held at 300 ℃ for 180 minutes to ensure complete burn-out of the polymer particles and to produce an at least substantially polymer-free grey part. The at least substantially polymer-free soot body part was heated from 300 ℃ to 1350 ℃ at a rate of 2.5 ℃/minute and held at 1350 ℃ for 240 minutes to sinter the at least substantially polymer-free soot body part and produce example part 2. Example part 2 was cooled from 1350 ℃ to room temperature at a rate of 5 ℃/min.

Example part 2 is shown in fig. 4B. The density of example part 2 was measured using the Archimedes technique and found to be 7.88g/cm³It is 8.0g/cm³98.5% of the bulk density of (c).

Reference throughout this specification to "one example," "another example," "an example," and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the example is included in at least one example described herein, and may or may not be present in other examples. Furthermore, it is to be understood that the described elements of any example may be combined in any suitable manner in different examples, unless the context clearly dictates otherwise.

It is to be understood that the ranges provided herein include the recited range and any value or subrange within the recited range. For example, a range of about 1 μm to about 200 μm should be interpreted to include the explicitly recited limits of about 5 μm to about 200 μm, as well as individual values, such as 7.15 μm, 15 μm, 65 μm, 100.5 μm, 125 μm, 195 μm, and the like, and sub-ranges, such as about 75 μm to about 175 μm, about 20 μm to about 125 μm, and the like. Further, when "about" is used to describe a value, it is meant to encompass minor variations (up to +/-10%) from the recited value.

In describing and claiming the examples disclosed herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

While multiple examples have been described in detail, it is to be understood that the disclosed examples can be modified. The foregoing description is, therefore, not to be taken in a limiting sense.

Claims (15)

1. A three-dimensional (3D) printing method, comprising:

applying a metallic build material;

selectively applying an adhesive fluid on at least a portion of the metal build material, the adhesive fluid comprising a liquid carrier and polymer particles dispersed in the liquid carrier, wherein the polymer particles each contain a low T_gHydrophobic component and high T_gA hydrophilic component, and wherein the high T_gThe hydrophilic component has a T above 25 ℃_gSaid low T_gThe hydrophobic component has a T of less than 25 DEG C_g；

Repeating the applying of the metallic build material and the selectively applying of the binder fluid to create a patterned green part;

heating the patterned green part to near the melting point of the polymer particles, thereby activating the binder fluid and generating a cured green part;

heating the cured green part to a thermal decomposition temperature of the polymer particles, thereby producing an at least substantially polymer-free gray part; and

heating the at least substantially polymer-free soot body part to a sintering temperature to form a metal part.

2. The method as defined in claim 1 wherein:

the polymer particles have a glass transition temperature (T) of 25 ℃ to 125 ℃_g)；

The melting point is 125 ℃ to 200 ℃;

the thermal decomposition temperature is 250 ℃ to 600 ℃; and

the sintering temperature is 850 ℃ to 1400 ℃.

3. The method as defined in claim 1 wherein:

heating the cured green part to a thermal decomposition temperature for a thermal decomposition time period of 30 minutes to 72 hours; and

heating the at least substantially polymer-free soot body part to a sintering temperature for a sintering time period of 20 minutes to 15 hours.

4. The method as defined in claim 1 wherein:

heating the cured green part to a thermal decomposition temperature is achieved at a rate of 0.5 ℃/minute to 10 ℃/minute; and

heating the at least substantially polymer-free ash blank component to the sintering temperature is accomplished at a rate of 1 ℃/minute to 20 ℃/minute.

5. The method as defined in claim 1, wherein heating the cured green body component to a thermal decomposition temperature and heating the at least substantially polymer-free ash body component to a sintering temperature is achieved in an environment containing an inert gas, a low reactivity gas, a reducing gas, or a combination thereof, wherein the low reactivity gas is nitrogen.

6. A method as defined in claim 5, wherein the environment further comprises carbon.

7. The method as defined in claim 1 wherein:

applying a metallic build material, selectively applying an adhesive fluid, repeating the applying and the selectively applying, and heating the patterned green part to about a melting point are completed on a build area platform; and

after heating the patterned green part to about the melting point, the method further comprises:

removing the cured green part from the build area platform; and are

Placing the cured green part in a heating mechanism.

8. The method as defined in claim 1 wherein the adhesive fluid further comprises a coalescing solvent selected from the group consisting of 2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol mono-n-butyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, diethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-n-butyl ether acetate, 2-methyl-1, 3-propanediol, and combinations thereof.

9. The method as defined in claim 8 wherein:

the polymer particles are present in the binder fluid in an amount of 2 to 30 wt%; and

the coalescing solvent is present in the binder fluid in an amount of 0.1 wt% to 50 wt%.

10. The method as defined in claim 1 wherein the method further comprises preparing the adhesive fluid by:

each polymer particle was prepared by one of the following methods:

(i) polymerization of low T_gHydrophobic monomers to form low T_gHydrophobic component, polymeric high T_gHydrophilic monomers to form high T_gHydrophilic component and high T_gAttachment of hydrophilic component to Low T_gOn the surface of the hydrophobic component; or

(ii) Low T at 5:95 to 30:70_gHydrophobic monomer pair high T_gRatio polymerization of hydrophilic monomers Low T_gHydrophobic monomers and high T_gA hydrophilic monomer; or

(iii) By low T_gThe hydrophobic monomer begins the polymerization process, followed by the addition of high T_gHydrophilic monomers and then ending the polymerization process, thereby at low T_gMaking higher concentrations at or near the surface of the hydrophobic componentHigh T of degree_gPolymerizing hydrophilic monomers; or

(iv) By low T_gHydrophobic monomers and high T_gThe hydrophilic monomer begins the copolymerization process, followed by the addition of an additional high T_gHydrophilic monomers and subsequently ending the copolymerization process, thereby at low T_gHigher concentration of high T at or near the surface of the hydrophobic component_gCopolymerization of hydrophilic monomers; and

the polymer particles are then added to a liquid carrier.

11. The method as defined in claim 10 wherein:

the low T_gThe hydrophobic monomer is selected from the group consisting of C4 to C8 alkyl acrylate monomers, C4 to C8 alkyl methacrylate monomers, styrene monomers, substituted methylstyrene monomers, vinyl ester monomers, and combinations thereof; and is

The high T_gThe hydrophilic monomer is selected from the group consisting of acidic monomers, unsubstituted amide monomers, alcohol acrylate monomers, alcohol methacrylate monomers, C1 to C2 alkyl acrylate monomers, C1 to C2 alkyl methacrylate monomers, and combinations thereof.

12. A method as defined in claim 1, wherein the selective application of the binder fluid is achieved by thermal inkjet printing or piezoelectric inkjet printing.

13. The method as defined in claim 1 wherein:

the metal build material is a powder having an average particle size of 10 to 150 μm;

the metal build material sintering into a continuous body to form the metal part when heated to a sintering temperature; and

the sintering temperature is lower than a melting point, a solidus temperature, a eutectic temperature, or a peritectic temperature of the metallic build material.

14. The method as defined in claim 1 wherein the metallic build material is applied in a layer having a thickness of 30 μ ι η to 300 μ ι η.

15. A three-dimensional (3D) printing system, comprising:

a metal build material supply;

building a material distributor;

a supply of adhesive fluid comprising a liquid carrier and polymer particles dispersed in the liquid carrier, wherein the polymer particles each contain a low T_gHydrophobic component and high T_gA hydrophilic component, and wherein the high T_gThe hydrophilic component has a T above 25 ℃_gSaid low T_gThe hydrophobic component has a T of less than 25 DEG C_g；

An ink-jet applicator for selectively dispensing the adhesive fluid;

at least one heat source;

a controller; and

a non-transitory computer-readable medium having stored thereon computer-executable instructions to enable the controller to:

iteratively forming a plurality of layers of metallic build material with the build material distributor and the inkjet applicator, which has applied and received a binder fluid through the build material distributor, thereby generating a patterned green part; and

utilizing the at least one heat source to:

heating the patterned green part to near the melting point of the polymer particles, thereby activating the binder fluid and generating a cured green part;

heating the cured green part to a thermal decomposition temperature of the polymer particles, thereby producing an at least substantially polymer-free gray part; and

heating the at least substantially polymer-free soot body part to a sintering temperature to form a metal part.

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